A novel method for the quantitative morphometric characterization of soluble salts on volcanic ash

<jats:title>Abstract</jats:title><jats:p>Formation of soluble sulfate and halide salts on volcanic ash particles via syn-eruptive interactions between ash surfaces and magmatic gases is a ubiquitous phenomenon in explosive eruptions. Surficial salts may be rapidly mobilized into their depositional environment undermining the quality of drinking water, harming aquatic life, and damaging soil and vegetation. Assessment of the potential for salt formation on ash and related environmental impacts have been based almost exclusively on bulk mineralogical or chemical analyses of ash; similarly, quantification of surficial salts has been made via leachate analysis only. However, it is the ash surface state and salt crystal properties that exert the predominant control on its reactivity, thus in determining their immediate environmental impact. Here, using scanning electron microscope (SEM) images, we present a novel image analysis protocol for the quantitative characterization of surficial salts, together with chemical analyses of resulting leachates. As volcanic ash proxies, we used synthetic rhyolitic glass particles (with systematic variations in FeO<jats:sub>T</jats:sub> and CaO content) and a crushed obsidian. Using an ash-gas reactor, we artificially surface-loaded samples with CaSO<jats:sub>4</jats:sub> and NaCl crystals, the most common crystal phases found on volcanic ash surfaces. Analogous variations were found using both methods: for CaSO<jats:sub>4</jats:sub> crystals, higher temperature treatments or increasing FeO<jats:sub>T</jats:sub> content at the same temperature led to higher concentrations of salt leachate and higher salt volumes; unexpectedly, increasing the CaO content caused only a minor increase in salt formation. In addition to bulk salt formation, morphometric results provided insight into formation processes, nucleation and growth rates, and limiting factors for salt formation. Higher temperatures increased CaSO<jats:sub>4</jats:sub> crystal size and surface coverage which we infer to result from higher element mobility in the glasses driving crystal growth. Increasing FeO<jats:sub>T</jats:sub> content of the glasses yielded increased salt surface coverage and leachate concentrations, but decreased crystal size (i.e., the salt number density increased). This latter effect likely relates to the role of iron as an electron-donor to charge balance salt-forming cation migration to the ash surface, indicating the importance of iron in determining surface reaction site density and, consequently, environmental reactivity. The controlling roles of ash composition and temperature on salt formation observed here can improve estimations for surface salt formation, volatile scavenging, and environmental impact for eruptions producing glass-rich ash. Our characterization protocol can therefore become a useful tool for the investigation of solid–gas reactions for terrestrial and planetary processes, and it also appears to be a powerful complement to research into atmospheric processes mediated by ash surfaces, such as ash aggregation and nucleation of water or ice on ash.</jats:p&gt

A novel method for the quantitative morphometric characterization of soluble salts on volcanic ash

Formation of soluble sulfate and halide salts on volcanic ash particles via syn-eruptive interactions between ash surfaces and magmatic gases is a ubiquitous phenomenon in explosive eruptions. Surficial salts may be rapidly mobilized into their depositional environment undermining the quality of drinking water, harming aquatic life, and damaging soil and vegetation. Assessment of the potential for salt formation on ash and related environmental impacts have been based almost exclusively on bulk mineralogical or chemical analyses of ash; similarly, quantification of surficial salts has been made via leachate analysis only. However, it is the ash surface state and salt crystal properties that exert the predominant control on its reactivity, thus in determining their immediate environmental impact. Here, using scanning electron microscope (SEM) images, we present a novel image analysis protocol for the quantitative characterization of surficial salts, together with chemical analyses of resulting leachates. As volcanic ash proxies, we used synthetic rhyolitic glass particles (with systematic variations in FeOT and CaO content) and a crushed obsidian. Using an ash-gas reactor, we artificially surface-loaded samples with CaSO4 and NaCl crystals, the most common crystal phases found on volcanic ash surfaces. Analogous variations were found using both methods: for CaSO4 crystals, higher temperature treatments or increasing FeOT content at the same temperature led to higher concentrations of salt leachate and higher salt volumes; unexpectedly, increasing the CaO content caused only a minor increase in salt formation. In addition to bulk salt formation, morphometric results provided insight into formation processes, nucleation and growth rates, and limiting factors for salt formation. Higher temperatures increased CaSO4 crystal size and surface coverage which we infer to result from higher element mobility in the glasses driving crystal growth. Increasing FeOT content of the glasses yielded increased salt surface coverage and leachate concentrations, but decreased crystal size (i.e., the salt number density increased). This latter effect likely relates to the role of iron as an electron-donor to charge balance salt-forming cation migration to the ash surface, indicating the importance of iron in determining surface reaction site density and, consequently, environmental reactivity. The controlling roles of ash composition and temperature on salt formation observed here can improve estimations for surface salt formation, volatile scavenging, and environmental impact for eruptions producing glass-rich ash. Our characterization protocol can therefore become a useful tool for the investigation of solid–gas reactions for terrestrial and planetary processes, and it also appears to be a powerful complement to research into atmospheric processes mediated by ash surfaces, such as ash aggregation and nucleation of water or ice on ash.Ludwig-Maximilians-Universität München (1024

Global role of the membrane protease LonB in Archaea: Potential protease targets revealed by quantitative proteome analysis of a lonB mutant in Haloferax volcanii

The membrane-associated LonB protease is essential for viability in Haloferax volcanii, however, the cellular processes affected by this protease in archaea are unknown. In this study, the impact of a lon conditional mutation (down-regulation) on H. volcanii physiology was examined by comparing proteomes of parental and mutant cells using shotgun proteomics. A total of 1778 proteins were identified (44% of H. volcanii predicted proteome) and 142 changed significantly in amount (≥. 2 fold). Of these, 66 were augmented in response to Lon deficiency suggesting they could be Lon substrates. The "Lon subproteome" included soluble and predicted membrane proteins expected to participate in diverse cellular processes. The dramatic stabilization of phytoene synthase (57 fold) in concert with overpigmentation of lon mutant cells suggests that Lon controls carotenogenesis in H. volcanii. Several hypothetical proteins, which may reveal novel functions and/or be involved in adaptation to extreme environments, were notably increased (300 fold). This study, which represents the first proteome examination of a Lon deficient archaeal cell, shows that Lon has a strong impact on H. volcanii physiology evidencing the cellular processes controlled by this protease in Archaea. Additionally, this work provides a platform for the discovery of novel targets of Lon proteases. Biological Significance: The proteome of a Lon-deficient archaeal cell was examined for the first time showing that Lon has a strong impact on H. volcanii physiology and evidencing the proteins and cellular processes controlled by this protease in Archaea. This work will facilitate future investigations aiming to address Lon function in archaea and provides a platform for the discovery of endogenous targets of the archaeal-type Lon as well as novel targets/processes regulated by Lon proteases. This knowledge will advance the understanding on archaeal physiology and the biological function of membrane proteases in microorganisms.Fil: Cerletti, Micaela. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Biológicas. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Biológicas; ArgentinaFil: Paggi, Roberto Alejandro. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Biológicas. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Biológicas; ArgentinaFil: Ramallo Guevara, Carina. Ruhr Universität Bochum; AlemaniaFil: Poetsch, Ansgar. Ruhr Universität Bochum; AlemaniaFil: de Castro, Rosana Esther. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata. Instituto de Investigaciones Biológicas. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales. Instituto de Investigaciones Biológicas; Argentin

Data in support of global role of the membrane protease LonB in Archaea: Potential protease targets revealed by quantitative proteome analysis of a lonB mutant in Haloferax volcanii

This data article provides information in support of the research article “Global role of the membrane protease LonB in Archaea: Potential protease targets revealed by quantitative proteome analysis of a lonB mutant in Haloferax volcanii” [1]. The proteome composition of a wt and a LonB protease mutant strain (suboptimal expression) in the archaeon Haloferax volcanii was assessed by a quantitative shotgun proteomic approach. Membrane and cytosol fractions of H. volcanii strains were examined at two different growth stages (exponential and stationary phase). Data is supplied in the present article. This study represents the first proteome examination of a Lon-deficient cell of the Archaea Domain

LonB protease Is a novel regulator of carotenogenesis controlling degradation of phytoene synthase in Haloferax volcanii

The membrane protease LonB is an essential protein in the archaeon Haloferax volcanii and globally impacts its physiology. However, natural substrates of the archaeal Lon protease have not been identified. The whole proteome turnover was examined in a H. volcanii LonB mutant under reduced and physiological protease levels. LC-MS/MS combined with stable isotope labeling was applied for the identification/quantitation of membrane and cytoplasm proteins. Differential synthesis and degradation rates were evidenced for 414 proteins in response to Lon expression. A total of 58 proteins involved in diverse cellular processes showed a degradation pattern (none/very little degradation in the absence of Lon and increased degradation in the presence of Lon) consistent with a LonB substrate, which was further substantiated for several of these candidates by pull-down assays. The most notable was phytoene synthase (PSY), the rate-limiting enzyme in carotenoid biosynthesis. The rapid degradation of PSY upon LonB induction in addition to the remarkable stabilization of this protein and hyperpigmentation phenotype in the Lon mutant strongly suggest that PSY is a LonB substrate. This work identifies for the first time candidate targets of the archaeal Lon protease and establishes proteolysis by Lon as a novel post-translational regulatory mechanism of carotenogenesis.Fil: Cerletti, Micaela. Universidad Nacional de Mar del Plata; ArgentinaFil: Paggi, Roberto Alejandro. Universidad Nacional de Mar del Plata; ArgentinaFil: Troetschel, Christian. Ruhr Universität Bochum; AlemaniaFil: Ferrari, María Celeste. Universidad Nacional de Mar del Plata; ArgentinaFil: Guevara, Carina Ramallo. Ruhr Universität Bochum; AlemaniaFil: Albaum, Stefan. Universitat Bielefeld; AlemaniaFil: Poetsch, Ansgar. Plant Biochemistry, Ruhr University Bochum; AlemaniaFil: de Castro, Rosana Esther. Universidad Nacional de Mar del Plata; Argentin

LonB Protease Is a Novel Regulator of Carotenogenesis Controlling Degradation of Phytoene Synthase in <i>Haloferax volcanii</i>

The membrane protease LonB is an essential protein in the archaeon <i>Haloferax volcanii</i> and globally impacts its physiology. However, natural substrates of the archaeal Lon protease have not been identified. The whole proteome turnover was examined in a <i>H. volcanii</i> LonB mutant under reduced and physiological protease levels. LC–MS/MS combined with stable isotope labeling was applied for the identification/quantitation of membrane and cytoplasm proteins. Differential synthesis and degradation rates were evidenced for 414 proteins in response to Lon expression. A total of 58 proteins involved in diverse cellular processes showed a degradation pattern (none/very little degradation in the absence of Lon and increased degradation in the presence of Lon) consistent with a LonB substrate, which was further substantiated for several of these candidates by pull-down assays. The most notable was phytoene synthase (PSY), the rate-limiting enzyme in carotenoid biosynthesis. The rapid degradation of PSY upon LonB induction in addition to the remarkable stabilization of this protein and hyperpigmentation phenotype in the Lon mutant strongly suggest that PSY is a LonB substrate. This work identifies for the first time candidate targets of the archaeal Lon protease and establishes proteolysis by Lon as a novel post-translational regulatory mechanism of carotenogenesis